ACTIVATION ENERGY VARIATION DURING IGNITION
OF PROPANE-AIR MIXTURES ON ISOTHERMALLY HEATED
PLATINUM FILAMENTS
D. Oancea ½, Maria Mitu½½, Domnina Razus½½
abstract: The ignition of a stagnant stoichiometric propane-air mixture by an isothermally
heated platinum filament supported on a thin quartz bar was studied at various filament
temperatures between 400 and 600 K and at ambient pressure. The heterogeneous ignition over
the platinum surface continues in the gaseous phase as an independent flame. The induction
periods of the gas-phase ignition at various filament temperatures were used to evaluate the
overall activation energy of the process.The chemical heat flux variation during surface reaction
exhibits an anti Arrhenius behaviour and allows an evaluation of a continuous change of the
apparent activation energy.
1. Introduction
The ignition of gaseous flammable mixtures on hot solid surfaces is a frequent phenomenon
having numerous implications and applications in a variety of combustion problems [1y3].
Special aspects connected with this subject arise from the catalytic effect of solid surfaces
[4y5]. Particularly, the catalytic oxidation of hydrocarbons on platinum has received wide
attention in recent years due to the use of platinum as one of the active components in
automotive exhaust catalytic converters. The experimental information and theoretical
analysis of the ignition indicate the existence of some critical conditions necessary for its
occurrence. A very specific property characterizing the system is the induction period of the
ignition and its dependence on the mixture pressure and composition as well as on the
surface temperature [5y7]. The variation of this property on the system variables gives
valuable information on the kinetics of process. The simple models which give the pressure
and composition dependence of the induction period reffer to initial gas composition,
before the ignition. Depending on the relative value of the induction period as well as on
the relative contribution of chemical reactions and transport processes, this composition can
be significantly changed. The aim of the present paper is to report the measured induction
periods of a stoichiometric propane-air mixture for gas-phase ignition on a heated platinum
filament at various filament temperatures and to calculate the overall activation energy and
its variation during this transient period. The ignition source, serving also as a detector of
½
½½
Department of Physical Chemistry, University of Bucharest, 4-12 Regina Elisabeta Blvd., 70346 Bucharest
“I.G.Murgulescu” Institute of Physical Chemistry, Spl.Independentei 202,
P.O.Box 12-194, 77208 Bucharest
Analele UniversităĠii din Bucureúti – Chimie, Anul XII (serie nouă), vol. I-II, pag. 243–250
Copyright © Analele UniversităĠii din Bucureúti
244
D. OANCEA “ MARIA MITU “ DOMNINA RAZUS
the processes accompanied by heat exchange, ensures a quasi-rectangular temperature
jump, followed by an isothermal heating. The fast response of the platinum filament with
respect to heat exchange processes is expected to give detailed information on the local
changes. The stoichiometric propane – air mixture was thoroughly examined in many
laboratories and there are reliable reference data in literature for comparison [4,8,9].
2. Experimental apparatus and procedure
The experimental equipment contains four major parts: (1) the gas feed and evacuation with
gas control and monitoring system, (2) the explosion cell equipped with a platinum filament
as ignition source, (3) the power supply and (4) the data acquisition system.
A specially designed electrical circuit is used to produce a quasi-rectangular jump of the
wire temperature and to keep it constant. A platinum wire coiled as filament with resistance
Rf, a standard resistor with resistance Rst and a potentiometer form a Wheatstone bridge.
The discharge of a condenser previously charged at a suitable voltage (established by trial
and error) across the filament in less than 1 ms insures the temperature jump, while an
integrated circuit senses the bridge unbalance and adjusts the feed voltage through a
transistor, permitting a continuous monitoring of Rf. The initial setting of potentiometer
adjusts the value of Rf and consequently the filament temperature [10,11]. The transient or
stationary voltages across Rst are recorded using a data acquisition system
Tektronix-TestLab 2505, provided with a 4-channel acquisition card type 25AA1.
To maintain the symmetry of the platinum filament, it was supported on a thin quartz bar
(I = 1 mm, l = 50 mm). Experiments were made at various filament temperatures (within
the range 437÷589 K), at a constant pressure (100 kPa) and stoichiometric composition
(4.02 vol.% propane) of propane-air mixture. The platinum filament temperature was
calculated from the circuit characteristics using the following equation taken from
literature:
U
A Bx Cx 2
(1)
where U = Rf/Rf0 is the relative resistance, Rf0 is the filament resistance at 0°C, x is the
temperature (in 0C) and A, B, C are constants (A = 1, B = 3.97427·10–3, C = 5.844·10–7 [12]).
3. Results and Discussion
The ignition on catalytically active surfaces is a complex process implying as a first step
the ignition of the surface reaction, occurring even outside the flammability limits of fuel,
followed subsequently by the gas phase ignition occurring within the explosivity range.
There is a strong interaction between surface and gas phase ignition [13y17]. While for
noncatalytic surfaces the combustion reaction is initiated within a thin layer of gas
surrounding the solid surface, for catalytic surfaces the process starts as a surface reaction
implying adsorbed species. When the critical conditions are attained, the gas phase reaction
propagates into the whole mixture. Since the combustion reactions in the adsorbed layer or
in the adjacent gas phase are exothermal, their occurrence can be easily identified on the
ACTIVATION ENERGY FOR IGNITION OF PROPANE-AIR MIXTURES
245
experimental curve giving the voltage across the standard resistor in time. The output of the
acquisition system for a typical run with the platinum filament on a quartz bar in air or in
the test mixture is given in Fig. 1 as voltage across the standard resistor, Ust in time. It can
be easily seen that the exothermic reactions can be identified as a lowering of the input
voltage necessary to maintain a constant temperature. The initial decreasing represents the
surface reaction, while the sudden decrease represents the ignition of the gas reaction.
8
in air
7
Uet / V
6
5
in explosive mixtures
4
W /2
W /10
W
3
2
0.0
0.1
0.2
0.3
0.4
0.5
0.6
time / s
Fig. 1: Output of the acquisition system for a typical run: voltage across the standard resistor, Ust
with the platinum filament on a quartz bar in air or in the test mixture
The data refer to a stoichiometric C3H8-air mixture at p0 = 100 kPa and T f = 1040 K.
On Ust = f(t) diagrams, the induction period can be measured as a function of the initial
pressure, p0, and the filament temperature, Tf. The thermal ignition theory indicates that the
induction period, IJi, can be expressed as a function of p0 and Tf by the relationship [1,17]:
Ea
Wi
a ˜ p0 n ˜ e RTf
(2)
where n is the overall reaction order, Ea is the activation energy, and R is the gas constant.
At constant pressure (100kPa) the following results were obtained from the plot lnW = f(1/T)
(Fig. 2): the slope = (9.06r1.36)×103, the intercept = –3.03r1.26 with the correlation
coefficient 0.968. The corresponding activation energy of the gas phase ignition process is
Ea = 75.3 kJ.mol–1 which can be compared with the reported data of Hiam, Wise and
Chaikin [4], who obtained Ea = 114 kJ.mol–1 and with the result from Veser and Schmidt
[8,9], who obtained Ea = 80 kJ.mol–1, for the surface ignition of propane-air stoichiometric
mixtures on platinum. Because of the relatively high values of the induction periods (up to
0.3 s) one can suppose that there is a significant change of mixture composition within the
D. OANCEA “ MARIA MITU “ DOMNINA RAZUS
246
reaction layer due to chemical reaction, so that the kinetics of the surface reaction might be
dependent on the variable local composition of mixture in time. It is also possible for the
surface combustion to change its mechanism between its start and the ignition of gas phase
reaction. All these processes are likely to induce a change of the overall activation
parameters. In order to check this posibility, we examined the heat flux (which is correlated
with the reaction rate) for different fractions of the induction period, for each surface
temperature. It is assumed that the induction period is a characteristic property of the
system and its fractions characterize also the process evolution in the same way for each
surface temperature. An examination of the heat flux for a specific fraction at different
temperatures would give a corresponding apparent activation energy.
5.8
5.7
5.6
ln W / (ms)
5.5
5.4
5.3
5.2
5.1
5.0
0.00088
0.00090
0.00092
0.00094
0.00096
K/T
Fig. 2: Induction periods of ignition for a stoichiometric C3H8-air mixture at p0 = 100 kPa
by a platinum filament supported on a quartz bar, at various temperatures
The difference between the rates of heat transfer from the filament to air and to an
explosive mixture originates essentially in the exothermic combustion reaction. The rate of
the chemical heat release dQr/dt can be considered equal to this difference and calculated as [10]:
d Qr d t
> U Rf
U st2
Rst2
air
2
st mixture
@
(3)
To visualize the variation of the activation energy during the transient period, the heat
fluxes for different fractions of the induction period (W/z, were 1<z<10) were calculated.
If dQr/dt is related to the rate of the overall combustion reaction, the following relationship
is obtained:
ACTIVATION ENERGY FOR IGNITION OF PROPANE-AIR MIXTURES
d Qr
dt D ˜
p0n
n1
˜ ( X ox
˜
X fn2
)˜e
Ea
RTf
247
(4)
where, as a first approximation, D is a constant, Xox and Xf are the molar fractions of oxygen
and fuel, respectively, and n1, n2 are the corresponding reaction orders. This relationship
can be used at the end of the ignition period, as well as for its different fractions and can be
also extrapolated to initial conditions, when the mixture composition within the reaction
layer is known. An illustrating plot at the end of induction period is given in Fig. 3 as
ln(dQr/dt) against 1/T. The correlation between the reaction heat flux and the surface
temperature is very good for such processes where there are many uncontrolled factors.
Similar analyses were made for different induction period fractions. The results are given in
Table 1. A systematic increase of the apparent activation energy from higher to lower
fractions can be observed. This variation is given in Fig. 4.
1.3
1.2
ln (dQ/dt)
1.1
1.0
0.9
0.8
0.7
0.00088
0.00090
0.00092
0.00094
0.00096
0.00098
K/T
Fig. 3: Rate of heat release at the surface ignition with a Pt filament supported on quartz
of a stoichiometric C3H8-air mixture at p0 = 100 kPa
An examination of the results given in Fig. 3 and 4, as well as those presented in Table 1,
indicates an anti Arrhenius dependence of ln(dQr/dt) with respect to 1/T which, according
to equation (4), should give a negative slope. A similar trend was also reported for a 4.47
vol% propylene/air mixture at normal pressure for temperatures between 1000 and 1200K
[19], using the same experimental technique. Such behaviour, although unusual, is not quite
surprising for a catalytic surface. Numerous experimental observations indicate that the
catalytic surfaces require higher ignition temperatures as compared to noncatalytic ones
[13y18], a result which contradicts the expected Arrhenius kinetics. It was shown [18] that
there are situations under which an increase in the surface temperature can result in an
inhibition of its ignition ability due to extensive reactant depletion within the adjacent
gaseous layer, enhanced by the catalytic effect. If the mass transfer is not able to
compensate rapidly this reactant deficit, the overall reaction rate can decrease with
D. OANCEA “ MARIA MITU “ DOMNINA RAZUS
248
temperature increasing. This possibility is explicitly shown in equation (4) through the
presence of the oxygen and fuel molar fractions, Xox and Xf. Within restricted experimental
conditions, when the mass transfer cannot compensate the reactant depletion, the decrease
X
of the product
n1
ox
˜ X fn2
can compensate the Arrhenius increase of the overall rate
constant. Consequently the reported values of the apparent activation energies represent
composite quantities containing both the overall activation energy and the temperature
variation of the local composition. In agreement with theoretical predictions [18], such
compensations are likely to occur especially for catalytic ignitions in stagnant mixtures.
350
300
Ea/kJ.mol
-1
250
200
150
100
50
0.0
0.2
0.4
0.6
0.8
1.0
fraction from the induction period
Fig. 4: Variation of the apparent activation energy against the fraction from the induction period,
for a stoichiometric C3H8-air mixture at p0 = 100 kPa
Table 1. Regression parameters of linearized form of equation (4) for different induction period fractions
Correlation
Slope
Intercept
Ea/kJ.mol-1
W/z
Coefficient
W/10
(37.9r12.6)103
-36.2r13.5
0.832
315r105
W/5
(30.5r5.11)103
-28.6r4.73
0.960
253r42.5
W/3
(19.9r3.36)103
-18.3r3.11
0.960
165r29.9
W/2
(13.9r1.74)103
-12.4r1.61
0.977
116r14.5
(10.7r1.52)10
3
-9.20r1.41
0.971
88.9r12.6
W/1.25
(9.27r1.30)10
3
-7.72r1.20
0.972
77.0r10.8
W/1
(6.87r0.596)103
-5.36r0.552
0.989
57.1r4.95
W/1.5
For many fuel/air mixtures, where the catalytic ignition occurs in flow systems, such
phenomena were not encountered. This can be explained by the renewal of reactant
concentrations brought about by convection. It is expected that a partial renewal of
ACTIVATION ENERGY FOR IGNITION OF PROPANE-AIR MIXTURES
249
reactants within the reaction zone can be also ensured by the natural convection that
supplements the mass transfer provided by the molecular diffusion. The variation of the
apparent activation energy within the ignition period indicates a higher effect of reactant
depletion at the beginning of the surface reaction, which subsequently decreases due
probably to natural convection. An important contribution to the decrease of the convection
mechanism, especially during the early stages, is likely to be brought by the presence of the
quartz bar used to support the platinum filament in order to maintain its symmetry. It
should be noted that small changes in experimental conditions could induce important
variations of the mass transport mechanism, explaining the large spread of data obtained in
this field.
Conclusions
The gas-phase ignition of a stoichiometric propane-air mixture was studied using an
isothermally heated platinum filament supported on a thin qurtz bar at different
temperatures and ambient pressure. The induction periods for different filament
temperatures were measured and the overall activation energy of the gas-phase ignition was
evaluated. The obtained value is close to other reported values for the surface ignition
process.From the analysis of the chemical heat flux during the transition from surface to
gas-phase ignition, an anti Arrhenius behaviour of the overall chemical reaction, as well as
a significant variation of the apparent activation energy for the surface reaction were found.
The results were explained assuming an important reactant depletion during the ignition
period, in accord with current opinions regarding the effects of catalytic surfaces at high
temperatures.
Acnowledgements
The authors acknowledge the financial support of the Romanian Ministry of Education and
Research under Research Grant nr.32/2002.
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